Resin composition, metal foil-clad laminated board and application of metal foil-clad laminated board

Abstract

The invention provides a resin composition, a metal foil-clad laminated board and application of the metal foil-clad laminated board. The resin composition comprises the following components in parts by mass: 10-40 parts of benzocyclobutenyl-containing organic silicon resin, 40-90 parts of a maleimide compound and 10-50 parts of other resin, the benzocyclobutenyl-containing organic silicon resin comprises any one or a combination of at least two of resins as shown in a formula I, a formula II and a formula III; the maleimide compound comprises an addition reaction product of a maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and an amine compound a2 containing at least two primary amino groups in one molecule. Through the design and compounding of the components, the resin composition and the plate containing the resin composition have the advantages of high glass transition temperature, low thermal expansion coefficient, low water absorption rate, excellent dielectric property, excellent heat resistance and excellent humidity and heat resistance, and can meet the performance requirements of high-frequency and high-speed packaging substrate materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of printed circuit board, and particularly relates to a resin composition, a metal-clad laminate and application thereof. BACKGROUND

[0002] With the development of miniaturization, multifunctionalization and rapid operation of electronic products, the integration of chips and semiconductor elements is higher and higher, and thus higher performance requirements are put forward for the substrate material carrying the semiconductor elements, such as the need to have excellent dielectric properties, dimensional stability, reliability, heat resistance and moisture resistance, etc.

[0003] At present, the resins used for substrate materials include epoxy resin, thermosetting polyphenyl ether resin, bismaleimide resin, hydrocarbon resin, etc. Among them, the epoxy resin has good heat resistance, chemical stability, mechanical properties, processing performance and cost advantage, and is once the most widely used resin material in circuit board, but its dielectric properties are poor, which is difficult to meet the development needs of high frequency and high speed in recent years. The thermosetting polyphenyl ether resin has been used for mass production of printed circuit board (PCB), and has good performance in mechanical properties and heat resistance, etc., but its dielectric constant and dielectric loss tangent are still high, which is difficult to meet the requirements of new generation communication technology. The dielectric properties of hydrocarbon resin are good, but its strength after curing is low, the glass transition temperature is low, the heat resistance is insufficient, and the adhesion performance is poor, and there are still many problems to be solved in practical application.

[0004] The bismaleimide resin has high reactivity, good fluidity and plasticity, and can be crosslinked and cured under the action of heating or catalysis. The cured product has high glass transition temperature, good heat resistance and stability, and can maintain high physical and mechanical properties in a wide temperature range. However, the cured product of the bismaleimide resin is brittle, has small bending modulus and insufficient flexibility, and the dielectric performance still has a large room for improvement. In order to improve the performance defects of the bismaleimide resin, polyphenyl ether, hydrocarbon resin and the like are usually introduced into the bismaleimide resin for modification. For example, CN111154197A discloses a resin composition comprising the following components: hydrocarbon resin 30-80 parts, bismaleimide resin 1-30 parts, polyphenyl ether resin 30-80 parts, initiator 0.1-5 parts, inorganic filler 20-60 parts, flame retardant 10-30 parts, and solvent 50-120 parts. The copper-clad plate prepared by impregnating glass cloth with the resin composition as a resin matrix has low dielectric constant and dielectric loss, good peel strength, high heat resistance and the like, and can be applied to high-frequency and high-speed fields. CN114437435A discloses a hydrocarbon resin-based prepreg comprising a reinforced cloth core and an external hydrocarbon resin layer, wherein the hydrocarbon resin layer comprises: hydrocarbon resin 20-40 parts, bismaleimide resin 10-20 parts, benzoxazine 5-10 parts, heat-conducting filler 5-10 parts, and curing agent 1-5 parts. The high-frequency copper-clad plate prepared by using the hydrocarbon resin-based prepreg has good dielectric properties. However, the compatibility of polyphenyl ether resin, hydrocarbon resin and the like with the bismaleimide resin is poor, the water absorption is large, and the heat resistance of the hydrocarbon resin itself is insufficient, and the thermal expansion coefficient is large, so that the physical properties of the resin composition containing the same are reduced, resulting in high thermal expansion coefficient of the copper-clad plate, serious warping, high water absorption, poor moisture resistance and heat resistance, insufficient dielectric performance, and difficulty in meeting the performance requirements of high-frequency and high-speed substrates.

[0005] Therefore, it is an urgent problem to be solved in the art to develop a resin material having low thermal expansion coefficient, low water absorption, high heat resistance and moisture resistance, and excellent dielectric performance, and a metal foil laminated board comprising the same. SUMMARY

[0006] In view of the deficiencies of the prior art, the purpose of the present application is to provide a resin composition, a metal foil laminated board and the application thereof. By designing specific maleimide compounds and specific structure of benzocyclobutene-based organic silicon resin and their mutual compounding with other resins, the components have excellent compatibility. The resin composition and the laminated board and the metal foil laminated board comprising the same have high glass transition temperature, low thermal expansion coefficient, low water absorption, low dielectric constant and low dielectric loss tangent, excellent heat resistance and moisture resistance, and can fully meet the performance requirements of high-frequency and high-speed packaging substrates.

[0007] To achieve the above object, the present application employs the following technical solutions:

[0008] In a first aspect, the present application provides a resin composition comprising the following components in parts by mass:

[0009] benzocyclobutene group-containing silicone resin 10-40 parts

[0010] maleimide compound 40-90 parts

[0011] other resin 10-50 parts;

[0012] The benzocyclobutene group-containing silicone resin includes any one of the resins shown in Formula I, Formula II, Formula III or a combination of at least two thereof.

[0013]

[0014] wherein R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from any one of hydrogen, C1-C18 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C13, C14, C15, C16, C17, etc.) straight chain or branched alkyl group, C3-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) cycloalkyl group, C2-C6 (e.g., C2, C3, C4, C5, etc.) alkenyl group, C6-C12 (e.g., C6, C9, C10, C12, etc.) aryl group, C2-C12 (e.g., C3, C4, C5, C6, C7, C8, C9, C10, C12, etc.) heteroaryl group.

[0015] m, p, a are each independently a number ≥2, e.g., can be 2, 3, 5, 8, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 180, or 200, etc., and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not exhaustively enumerate the specific point values included in the range.

[0016] n, q, b are each independently a number ≥0, e.g., can be 1, 2, 3, 5, 8, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 180, or 200, etc., and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not exhaustively enumerate the specific point values included in the range.

[0017] The maleimide compound includes an additive of a maleimide compound a1 containing at least 2 N-substituted maleimide groups in 1 molecule and an amine compound a2 containing at least 2 primary amino groups in 1 molecule.

[0018] The resin composition provided by this invention comprises a specific mass fraction of a combination of a benzocyclobutene-containing organosilicon resin, a maleimide compound, and other resins. The specific structural and property characteristics of each component are as follows:

[0019] The benzocyclobutene-containing organosilicon resin includes any one or a combination of at least two of the resins shown in Formula I, Formula II, and Formula III. Its side chain contains a benzocyclobutyl structure, which has excellent reactivity and can undergo cross-linking reaction to form a dense cross-linked network structure. It can obtain better dielectric properties through thermosetting. At the same time, the main chain of the organosilicon resin contains -Si-O- bonds, which has good mechanical properties, flexibility, and heat resistance.

[0020] It should be noted that the organosilicon resin containing benzocyclobutene can be understood as a copolymer, which includes structural units containing benzocyclobutene. and structural units that do not contain benzocyclobutene The connection order of structural units containing benzocyclobutene and structural units not containing benzocyclobutene is not limited, and any connection order / connection method that is chemically feasible is within the scope of this invention; exemplary examples include, but are not limited to, random copolymers, block copolymers, etc.

[0021] The maleimide compound, specifically a maleimide-modified compound, comprises an addition reaction product of a maleimide compound a1 containing at least two (e.g., two, three, or four) N-substituted maleimide groups in one molecule and an amine compound a2 containing at least two (e.g., two, three, four, or five) primary amino groups in one molecule. The maleimide compound can be understood as a mixture of maleimides, including maleimide addition reaction monomers, maleimide addition reaction oligomers or polymers, and maleimide monomers, maleimide oligomers or polymers that have not participated in the addition reaction. The maleimide compound contains primary amino, secondary amino, and carbon-carbon double bonds, exhibits high reactivity, and after curing, possesses high heat resistance and a low coefficient of planar thermal expansion.

[0022] The other resins are resins different from the organosilicon resins containing benzocyclobutene and the maleimide compounds, preferably thermosetting resins, which can chemically react with the organosilicon resins containing benzocyclobutene and the maleimide compounds to jointly construct the cross-linked network structure of the cured resin composition.

[0023] This invention solves the problem of poor compatibility between bismaleimide resin and other polymers by designing a specific structure of benzocyclobutene-containing organosilicon resin and a specific component of maleimide compound, and by combining them with other resins, thus achieving excellent compatibility among the components. The organosilicon resin and maleimide compound contain numerous reaction sites and high reactivity. They synergistically interact and, when combined with other resins, can undergo cross-linking reactions, increasing the cross-linking density of the resin composition. This results in a cured product with a high glass transition temperature, low coefficient of thermal expansion, low water absorption, low dielectric constant, and low dielectric loss tangent. This solves the problems of insufficient dielectric properties and high water absorption in maleimide-based resin compositions, as well as the problems of increased coefficient of thermal expansion and decreased heat resistance commonly found when maleimide compounds are combined with low-dielectric resins. Consequently, the resin composition and laminates containing it, including metal foil laminates, exhibit excellent heat resistance, damp heat resistance, dielectric properties, and dimensional stability, fully meeting the performance requirements of high-speed packaging substrate materials.

[0024] In the resin composition provided by the present invention, the organosilicon resin containing benzocyclobutene group has a mass part of 10-40 parts, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts or 38 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0025] The maleimide compound is in the range of 40-90 parts by mass, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 85 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0026] The other resins are in the range of 10-50 parts by weight, for example, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0027] The terms "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0028] In this invention, the benzocyclobutene-containing silicone resin, maleimide compound, and other resins are compounded in the aforementioned specific mass proportions to give the resin composition and the laminate and metal foil-coated laminate containing it high glass transition temperature, low coefficient of thermal expansion, low water absorption, low dielectric constant, low dielectric loss tangent, excellent heat resistance, resistance to damp heat, and dielectric properties. If the amount of benzocyclobutene-containing silicone resin is too low, at a similar amount of maleimide compound, the coefficient of thermal expansion of the resin composition will increase, and the resistance to deformation will decrease. Conversely, if the amount of benzocyclobutene-containing silicone resin is too low, resulting in an excessive amount of maleimide compound, the water absorption and D of the resin composition will decrease. f The coefficient of thermal expansion tends to increase, while the resistance to damp heat and dielectric properties decrease. If the amount of benzocyclobutene-containing silicone resin is too high, the dielectric loss of the resin composition will be too high and the dielectric properties will decrease. If the amount of maleimide compound is too low due to the excessive amount of benzocyclobutene-containing silicone resin, the coefficient of thermal expansion of the resin composition tends to increase and the resistance to deformation will be worse.

[0029] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0030] In this invention, the C1-C18 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C13, C14, C15, C16, C17, and C18, and exemplary include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc., preferably C1-C4 straight-chain or branched alkyl groups and C8-C17 straight-chain or branched alkyl groups.

[0031] In this invention, the C3-C10 cycloalkyl group can be a cycloalkyl group of C3, C4, C5, C6, C7, C8, C9, or C10, including monocycloalkyl or polycycloalkyl groups, and exemplary including but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0032] In this invention, the C2-C6 alkenyl group can be a straight-chain or branched alkenyl group of C2, C3, C4, C5, or C6, and the structure contains at least one C=C, including but not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, etc.

[0033] In this invention, the C6-C12 aryl group can be a monocyclic aryl or fused-ring aryl group of C6, C9, C10, C1, etc., and exemplary includes, but is not limited to: phenyl, biphenyl, naphthyl, anthracene, phenanthrene, etc.

[0034] In this invention, the C2-C12 heteroaryl group can be a heteroaryl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, or C12, containing at least one heteroatom, including N, O, S, etc., including monocyclic heteroaryl or fused-ring heteroaryl groups, and exemplary including but not limited to: pyridinyl, furanyl, thiophene, pyrroleyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothiophene, carbazoleyl, N-phenylcarbazoleyl, etc.

[0035] Preferably, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from any one of C1-C12 straight-chain or branched alkyl, C2-C4 alkenyl, and C6-C12 aryl, and more preferably any one of methyl, ethyl, n-propyl, isopropyl, allyl, phenyl, and dodecyl.

[0036] Preferably, in Formula I, 0.1 ≤ m / (m+n) ≤ 0.8. For example, m / (m+n) can be 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0037] Preferably, in Formula II, 0.1 ≤ p / (p+q) ≤ 0.8. For example, p / (p+q) can be 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0038] Preferably, in Formula III, 0.1 ≤ a / (a+b) ≤ 0.8. For example, a / (a+b) can be 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0039] As a preferred embodiment of the present invention, the organosilicon resin containing benzocyclobutene groups has a molar fraction of benzocyclobutene structural units of 0.1-0.8, thereby giving the organosilicon resin excellent reactivity, dielectric properties, flexibility, and heat resistance. When compounded with maleimide compounds and other resins and undergoing cross-linking reactions, it can form a dense cross-linked network structure in the cured product, improving the heat resistance, damp heat resistance, dielectric properties, and mechanical properties of the resin composition. If the molar fraction of benzocyclobutene structural units in the organosilicon resin is too low, the cross-linking density of the cured product will be reduced, affecting the glass transition temperature and heat resistance of the resin composition. If the molar fraction of benzocyclobutene structural units in the organosilicon resin is too high, not only will the flexibility of the resin composition and the sheet containing it be reduced, but unreacted benzocyclobutene groups will remain in the resin composition. These remaining benzocyclobutene groups will further react, generating stress and affecting reliability.

[0040] Preferably, the number average molecular weight of the organosilicon resin containing benzocyclobutene is 500-20000, for example, it can be 1000, 2000, 3000, 4000, 5000, 6000, 8000, 10000, 12000, 14000, 15000, 16000 or 18000, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0041] Preferably, the maleimide compound a1 contains two N-substituted maleimide groups in one molecule.

[0042] Preferably, the maleimide compound a1 includes N,N'-ethylidene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,3-(2-methylphenylene))bismaleimide, N,N'-(1,3-(4-methylphenylene))bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimide-phenyl)methane, bis(3-methyl-4-maleimide-phenyl)methane, bis(3,5-dimethyl-4-maleimide-phenyl)methane, and bis(3-ethyl-5-methyl-4-maleimide-phenyl) Methane, bis(3-ethyl-4-maleimide-phenyl)methane, bis(3,5-diethyl-4-maleimide-phenyl)methane, bis(4-maleimide-phenyl) ether, bis(4-maleimide-phenyl) ketone, bis(4-maleimide-cyclohexyl)methane, 1,4-bis(4-maleimide-phenyl)cyclohexane, 1,4-bis(maleimide-methyl)cyclohexane, 1,4-bis(maleimide-methyl)benzene, 1,3-bis(4-maleimide-phenoxy)benzene, 1,3-bis(3-maleimide-phenoxy)benzene, bis(4-(3-maleimide-phenoxy)phenyl)methane, bis(4-(4-maleimide-phenyl) 1,1-bis(4-(3-maleiminophenoxy)phenyl)ethane, 1,1-bis(4-(4-maleiminophenoxy)phenyl)ethane, 1,2-bis(4-(3-maleiminophenoxy)phenyl)ethane, 1,2-bis(4-(4-maleiminophenoxy)phenyl)ethane, 2,2-bis(4-(3-maleiminophenoxy)phenyl)propane, 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane, 2,2-bis(4-(3-maleiminophenoxy)phenyl)butane, 2,2-bis(4-(4-maleiminophenoxy)phenyl)butane, 4,4' -A combination of any one or at least two of bis(3-maleiminophenoxy)biphenyl, 4,4'-bis(4-maleiminophenoxy)biphenyl, bis(4-(3-maleiminophenoxy)phenyl)one, bis(4-(4-maleiminophenoxy)phenyl)one, bis(4-(3-maleiminophenoxy)phenyl)ether, and bis(4-(4-maleiminophenoxy)phenyl)ether, further preferably any one or at least two of bis(3-ethyl-5-methyl-4-maleiminophenyl)methane, bis(4-maleiminophenyl)methane, and 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane.

[0043] Preferably, the amine compound a2 comprises a siloxane compound containing at least two primary amino groups, diaminobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,3'-diethyl-4,4'-diaminodiphenylmethane. 4'-Diaminodiphenylmethane, 3,3'-Diethyl-5,5'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-5,5'-Diethyl-4,4'-Diaminodiphenylmethane, diaminodiphenyl ether, 3,3'-Dimethoxy-4,4'-Diaminodiphenyl ether, 3,3'-Dimethyl-4,4'-Diaminodiphenyl ether, 3,3'-Dimethyl-5,5'-Dimethyl-4,4'-Diaminodiphenyl ether, 3,3'-Diethyl-4,4'-Diaminodiphenyl ether, 3,3'-Diethyl-5,5'-Diethyl 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl; further The preferred step involves any one or a combination of at least two of the following: a siloxane compound containing at least two primary amino groups; 3,3'-dimethyl-4,4'-diaminodiphenylmethane; 3,3'-dimethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane; 3,3'-diethyl-4,4'-diaminodiphenylmethane; 3,3'-diethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane; 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane; and 2,2-bis(4-(4-aminophenoxy)phenyl)propane.

[0044] Exemplary examples include commercially available siloxane compounds containing two primary amino groups, such as, but not limited to, PAM-E (side-chain methyl type, functional group equivalent 130 g / mol), KF-8010 (side-chain methyl type, functional group equivalent 430 g / mol), X-22-161A (side-chain methyl type, functional group equivalent 800 g / mol), and X-22-161B (side-chain methyl type, functional group equivalent 800 g / mol) from Shin-Etsu Chemical Industry Co., Ltd. The functional group equivalent is 1500 g / mol), KF-8012 (side chain methyl type, functional group equivalent 2200 g / mol), KF-8008 (side chain methyl type, functional group equivalent 5700 g / mol), X-22-9409 (side chain phenyl type, functional group equivalent 670 g / mol), and X-22-1660B-3 (side chain phenyl type, functional group equivalent 2200 g / mol).

[0045] Preferably, the addition reaction of maleimide compound a1, which contains at least two N-substituted maleimide groups in one molecule, and amine compound a2, which contains at least two primary amino groups in one molecule, is carried out in an organic solvent; the type of organic solvent is not particularly limited, but propylene glycol monomethyl ether is more preferably preferred.

[0046] In this invention, the addition reaction temperature of maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and amine compound a2 containing at least two primary amino groups in one molecule is not particularly limited, as long as maleimide compound a1 and amine compound a2 react. As a preferred technical solution of this invention, from the perspective of reaction rate and solvent boiling point, the temperature of the addition reaction is 100-130℃, for example, 102℃, 105℃, 108℃, 110℃, 112℃, 115℃, 118℃, 120℃, 122℃, 125℃ or 128℃, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0047] In this invention, the addition reaction time of maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and amine compound a2 containing at least two primary amino groups in one molecule is not particularly limited. Preferably, the addition reaction time is 2-10 h, for example, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range. More preferably, it is 3-8 h.

[0048] Preferably, the other resins include any one or a combination of at least two of epoxy resins, acid anhydride compounds, reactive ester compounds, cyanate ester compounds, and compounds having carbon-carbon unsaturated double bonds in their molecules, and more preferably compounds having carbon-carbon unsaturated double bonds in their molecules.

[0049] Preferably, the compound having carbon-carbon unsaturated double bonds within its molecule includes any one or a combination of at least two of the following: unsaturated polyphenylene ether, polyfunctional vinyl compounds, allyl compounds, acrylate compounds, acenaphthene compounds, and polybutadiene.

[0050] Preferably, the unsaturated polyphenylene ether comprises polyphenylene ethers with unsaturated groups at the end; wherein the unsaturated groups can be any one or a combination of at least two of vinylbenzyl, vinylphenyl, acrylate, and methacrylate groups.

[0051] Preferably, the resin composition further comprises 5-30 parts by weight of a thermoplastic polymer, wherein the parts by weight of the thermoplastic polymer may be 8, 10, 12, 15, 18, 20, 22, 25, or 28 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0052] Preferably, the thermoplastic polymer includes any one or a combination of at least two of styrene-based polymers, hydrogenated styrene-based polymers, and polyolefin resins.

[0053] Preferably, the styrene-based polymer is a copolymer comprising olefin structural units and styrene-based structural units. The olefin structural units are derived from olefin monomers, such as structural units derived from butadiene or isoprene; the styrene-based structural units are derived from styrene monomers, such as structural units derived from styrene or structural units derived from styrene with substituents. In addition to containing olefin and styrene-based structural units, the styrene-based polymer may also contain structural units other than olefin and styrene-based structural units, such as structural units containing epoxy groups, amino groups, or maleic anhydride groups.

[0054] It should be noted that the styrene-based polymer can be a random copolymer or a block copolymer.

[0055] Preferably, the hydrogenated styrene polymer is obtained by partially or completely hydrogenating the structural units of the aforementioned styrene polymer derived from olefins.

[0056] The styrene-based polymers and hydrogenated styrene-based polymers may be commercially available products, including but not limited to: any one or a combination of at least two of Ricon 100 (butadiene-styrene copolymer, Cray Valley), Ricon 181 (butadiene-styrene copolymer, Cray Valley), Tuftec H1051 (hydrogenated styrene-butadiene copolymer with a styrene content of 42% by mass, Asahi Kasei Chemicals Co., Ltd.), and Tuftec M1913 (hydrogenated styrene-butadiene copolymer with maleic anhydride structural units, with a styrene content of 30% by mass, Asahi Kasei Chemicals Co., Ltd.).

[0057] Preferably, the resin composition further comprises 0.01-5 parts by weight of a curing accelerator, wherein the curing accelerator may be 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 4.8 parts by weight, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0058] Preferably, the curing accelerator includes any one or a combination of at least two of the following: acidic curing accelerators, organophosphorus curing accelerators, imidazole curing accelerators, pyridine curing accelerators, amine curing accelerators, peroxides, and organometallic salts.

[0059] Exemplary examples include acidic curing accelerators such as p-toluenesulfonic acid; organophosphorus curing accelerators such as triphenylphosphine; imidazole curing accelerators such as imidazole and / or imidazole derivatives (e.g., 2-methylimidazolium, 2-ethylimidazolium, 2-ethyl-4-methylimidazolium, etc.); pyridine curing accelerators such as pyridine and / or pyridine derivatives (e.g., 4-dimethylaminopyridine); amine curing accelerators such as secondary amine compounds, tertiary amine compounds, quaternary ammonium salts, etc.; and peroxides such as organic peroxides, including but not limited to: dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyn-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, or α,α'-bis(tert-butylperoxy)dicumyl peroxide, etc.; and organometallic salts such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, etc. The curing accelerators can be used alone or in combination of at least two.

[0060] Preferably, the resin composition further comprises 5-250 parts by weight of inorganic filler, wherein the parts by weight of the inorganic filler may be 8, 10, 20, 30, 50, 70, 90, 100, 110, 130, 150, 170, 190, 200, 220 or 240 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0061] This invention does not particularly limit the type of inorganic filler, but exemplary examples include, but are not limited to, any one or a combination of at least two of the following: silica, aluminum hydroxide, magnesium hydroxide, boehmite, molybdenum oxide, zinc oxide, zinc molybdate, zinc borate, zinc stannate, titanium dioxide, strontium titanate, barium titanate, barium sulfate, clay, kaolin, talc, mica, boron nitride, aluminum nitride, silicon carbide, alumina, composite silica powder, glass powder, short glass fiber, and hollow glass. To improve the heat resistance, damp heat resistance, and dimensional stability of the resin composition, it is preferred to include any one or a combination of at least two of the following: silica, aluminum hydroxide, magnesium hydroxide, boehmite, boron nitride, aluminum nitride, silicon carbide, alumina, composite silica powder, glass powder, short glass fiber, and hollow glass. The silica can be any one or a combination of at least two of the following: crystalline silica, fused silica, amorphous silica, spherical silica, and hollow silica, and is more preferably spherical silica.

[0062] The average particle size (D) of inorganic fillers 50 There are no specific limitations; from the perspective of dispersibility, the average particle size (D) 50 The preferred particle size distribution (PPD) is 0.01-20 μm, for example, it can be 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, or 18 μm, as well as specific values ​​between the above values. For space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range, but 0.01-10 μm is further preferred. Different types of inorganic fillers with different particle size distributions or different average particle sizes can be used alone or in combination as needed.

[0063] For example, the particle size of the inorganic filler was obtained using an MS3000 Malvern laser particle size analyzer.

[0064] Preferably, the inorganic filler includes a surface-treated filler, and the surface treatment agent includes any one or a combination of at least two of silane coupling agents, organosilicon oligomers, and titanate coupling agents, with silane coupling agents being more preferred.

[0065] Preferably, the resin composition further comprises 2-50 parts by weight of flame retardant, wherein the flame retardant may be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts by weight, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0066] This invention does not particularly limit the flame retardant, which can be selected from halogenated or non-halogenated flame retardants that are soluble or insoluble in organic solvents. For example, the non-halogenated flame retardant includes inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, metal hydrates, etc.

[0067] From the perspective of environmental protection and excellent dielectric properties, flame retardants preferably include organophosphorus flame retardants. For example, the organophosphorus flame retardants include aromatic phosphates, monosubstituted phosphonate diesters, disubstituted hypophosphite esters, metal salts of disubstituted hypophosphite acids, organic nitrogen- and phosphorus-containing compounds, cyclic organophosphorus compounds, etc.

[0068] For example, the aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, tri(xyl) phosphate, toluene diphenyl phosphate, toluene di-2,6-xylene phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di(2,6-dimethylphenyl) phosphate), 4,4'-biphenyl bis(di(2,6-dimethylphenyl) phosphate), bisphenol A-bis(di(2,6-dimethylphenyl) phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate), etc.; the monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, etc.; the disubstituted hypophosphonates include Diphenylphosphine ester, methyl diphenylphosphine ester, etc.; the metal salts of the disubstituted phosphine acids include metal salts of dialkylphosphine acids, metal salts of diallylphosphine acids, metal salts of divinylphosphine acids, metal salts of diarylphosphine acids, metal salts of diarylphosphine acids, etc.; the organic nitrogen-phosphorus compounds include phosphazene compounds, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, etc.; the cyclic organophosphorus compounds include 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Flame retardants can be used alone or in combination of at least two.

[0069] Preferably, the resin composition further comprises 0.01-10 parts by weight of coupling agent, wherein the parts by weight of coupling agent may be 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0070] Preferably, the coupling agent comprises a silane coupling agent.

[0071] This invention does not specifically limit the type of silane coupling agent, but includes, by way of example, any one or a combination of at least two of the following: epoxy silane coupling agents, amino silane coupling agents, vinyl silane coupling agents, styryl silane coupling agents, isobutylene silane coupling agents, propylene silane coupling agents, urea silane coupling agents, mercapto silane coupling agents, chloropropyl silane coupling agents, sulfur-based silane coupling agents, and isocyanate-based silane coupling agents.

[0072] Solvents may also be added to the resin composition. The amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition reaches a suitable viscosity for use, facilitating coating, impregnation, and processing. During subsequent drying, semi-curing, or complete curing stages, the solvent in the resin composition will partially or completely evaporate.

[0073] The solvent used in this invention is not particularly limited, and generally can be ketones such as acetone, butanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, or butanol; alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone. The solvent can be used alone or in mixtures of two or more. Preferably, ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are used.

[0074] The resin composition provided by the present invention is prepared by the following method, the preparation method comprising: mixing and dispersing the components in the resin composition evenly to obtain the resin composition.

[0075] In a second aspect, the present invention provides a resin film, the material of which comprises the resin composition as described in the first aspect.

[0076] Preferably, the resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

[0077] Preferably, the drying and semi-curing temperatures are each independently between 100-180℃, for example, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, or 175℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0078] Thirdly, the present invention provides a resin-coated copper foil, the resin-coated copper foil comprising a copper foil layer and a resin layer, wherein the material of the resin layer comprises the resin composition as described in the first aspect.

[0079] Preferably, the resin-coated copper foil is obtained by coating the resin composition onto a copper foil and then drying and / or semi-curing it.

[0080] Preferably, the drying and semi-curing temperatures are each independently between 100-180℃, for example, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, or 175℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0081] Fourthly, the present invention provides a prepreg comprising a substrate and a resin composition as described in the first aspect attached to the substrate.

[0082] Preferably, the resin composition is adhered to the substrate after impregnation and drying.

[0083] Preferably, the raw materials of the substrate include any one or at least two combinations of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers; for example, glass fiber cloth, organic fiber cloth, glass fiber paper, quartz glass fiber blended cloth, non-woven fabric, quartz cloth, wood pulp paper, etc.

[0084] Preferably, the fiberglass cloth includes any one or a combination of at least two of Q-fiberglass cloth, E-fiberglass cloth, D-fiberglass cloth, L-fiberglass cloth, M-fiberglass cloth, S-fiberglass cloth, T-fiberglass cloth, and NE-fiberglass cloth.

[0085] Preferably, the organic fiber cloth includes any one or a combination of at least two of polyimide fiber cloth, polyamide fiber cloth, polyester fiber cloth, polyphenylene ether fiber cloth, and liquid crystal polymer fiber cloth.

[0086] For example, the prepreg is prepared by impregnating a substrate with the resin solution of the resin composition and then drying it to obtain the prepreg.

[0087] Preferably, the solvent of the resin adhesive includes any one or a combination of at least two of acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene, and xylene.

[0088] Preferably, the drying temperature is 100-180℃, for example, it can be 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃ or 175℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0089] Preferably, the drying time is 1-30 min, for example, it can be 2 min, 5 min, 8 min, 10 min, 15 min, 20 min or 25 min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0090] Fifthly, the present invention provides a laminate comprising at least one prepreg as described in the fourth aspect.

[0091] In a sixth aspect, the present invention provides a metal foil laminate, the metal foil laminate comprising at least one of the following: a resin film as described in the second aspect, a resin-coated copper foil as described in the third aspect, and a prepreg as described in the fourth aspect.

[0092] Preferably, the metal foil in the metal foil-coated laminate includes any one or a combination of at least two of copper foil, aluminum foil, nickel foil, and alloy foil, with copper foil being more preferred.

[0093] Wherein, the metal foil is copper foil, and the metal foil laminate is copper clad laminate.

[0094] Preferably, the number of prepreg sheets in the metal foil laminate is 1-20, for example, 2, 3, 5, 7, 9, 10, 11, 13, 15, 17 or 19, and the specific point values ​​between the above point values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0095] For example, the method for preparing the metal foil laminate includes: pressing a metal foil onto one or both sides of a prepreg and curing it to obtain the metal foil laminate; or, stacking at least two prepregs into a laminate, then pressing a metal foil onto one or both sides of the laminate and curing it to obtain the metal foil laminate.

[0096] Preferably, the curing is carried out in a press.

[0097] Preferably, the curing temperature is 170-280℃, such as 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃ or 270℃, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 200-250℃ is further preferred.

[0098] Preferably, the curing pressure is 10-60 kg / cm². 2 For example, it can be 15kg / cm 2 20kg / cm 2 25kg / cm 2 30kg / cm 2 35kg / cm 2 40kg / cm 2 45kg / cm 2 50kg / cm 2 Or 55kg / cm 2 As well as the specific point values ​​between the above point values, due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0099] Preferably, the curing time is 30-300 min, for example 40 min, 60 min, 80 min, 100 min, 120 min, 150 min, 180 min, 200 min, 220 min, 240 min, 260 min or 280 min, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 30-180 min is further preferred.

[0100] In a seventh aspect, the present invention provides a printed circuit board, the printed circuit board comprising at least one of the following: a resin film as described in the second aspect, a resin-coated copper foil as described in the third aspect, a prepreg as described in the fourth aspect, a laminate as described in the fifth aspect, and a metal foil-coated laminate as described in the sixth aspect.

[0101] Compared with the prior art, the present invention has the following beneficial effects:

[0102] (1) The resin composition provided by the present invention, with its specific structure of benzocyclobutene-containing organosilicon resin, specific component of maleimide compound and its mutual compounding with other resins, solves the problems of poor compatibility of maleimide resin with other polymers, insufficient dielectric properties and high water absorption of resin composition with maleimide resin as the main body. It also solves the problems of increased thermal expansion coefficient and poor heat resistance that are common when maleimide compound is combined with low dielectric resin. The resin composition has excellent compatibility and high crosslinking density. The cured product and the laminate and metal foil laminate containing it have high glass transition temperature, low thermal expansion coefficient, low water absorption, low dielectric constant and low dielectric loss tangent, excellent heat resistance, damp heat resistance and dielectric properties. It is especially suitable for fields with high requirements for thermal expansion coefficient, heat resistance and dielectric loss under different environments, such as high-speed packaging substrate materials.

[0103] (2) Through the component design and optimization of the resin composition, the present invention enables the prepared metal foil laminate to achieve a dielectric constant D of 10 GHz. k ≤3.61, dielectric loss tangent D f ≤0.0037, the tangent of the dielectric loss angle D after moisture absorption f With a variation value ≤0.0005, a coefficient of thermal expansion XY-CTE ≤11ppm / ℃, a glass transition temperature Tg of 235-281℃, a water absorption rate ≤0.17%, and a pressure cooking test (PCT) that meets the requirement of at least 5 hours, it possesses a low coefficient of thermal expansion, low water absorption rate, excellent dielectric properties, heat resistance, and damp heat resistance, fully meeting the performance requirements of high-speed packaging substrate materials. Detailed Implementation

[0104] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0105] The materials involved in the following specific embodiments of the present invention are as follows:

[0106] (1) Organosilicon resins containing benzocyclobutene groups

[0107] The organosilicon resin A1 containing benzocyclobutene group has the structure shown in Formula I, and its preparation method includes:

[0108] Under a nitrogen atmosphere, 2.64 g of magnesium shavings, 0.05 g of iodine, and 30 mL of tetrahydrofuran were added to a dry three-necked flask. While stirring, 30 mL of a tetrahydrofuran solution containing 18.3 g of 4-bromo-benzocyclobutene resin was added dropwise. The reaction mixture was stirred at 50 °C for 2 h. Then, 15 mL of a tetrahydrofuran solution containing 15.8 g of dimethyldiethoxysilane and methyltriethoxysilane was added dropwise. The reaction mixture was stirred at 70 °C for 5 h. After cooling to room temperature, the reaction mixture was quickly poured into petroleum ether, impurities were filtered out, and vacuum distilled to obtain a mixture of benzocyclobutenyldimethylethoxysilane and benzocyclobutenylmethyldiethoxysilane. 50 mL of ethanol, 0.0 2g of tetramethylamine hydroxide and 5mL of water were mixed evenly, and a mixture of 6.18g of benzocyclobutenyldimethylethoxysilane and benzocyclobutenylmethyldiethoxysilane and 4.44g of dimethyldiethoxysilane were added. The mixture was stirred at 60℃ for 4h, cooled to room temperature, washed with water until neutral, dried with anhydrous sodium sulfate, filtered to remove toluene, and heated under reduced pressure to 150℃ / 10MPa to remove small molecule compounds, yielding organosilicon resin A1 containing benzocyclobutenyl groups.

[0109] Organosilicon resin A2 containing benzocyclobutene group has the structure shown in Formula II, and is prepared by the following method:

[0110] Under a nitrogen atmosphere, 2.64 g of magnesium shavings, 0.05 g of iodine, and 30 mL of tetrahydrofuran were added to a dry three-necked flask. While stirring, 30 mL of a tetrahydrofuran solution containing 27.1 g of 4-bromo-benzocyclobutene resin was added dropwise. The mixture was stirred at 50 °C for 2 h. Then, 15 mL of a tetrahydrofuran solution containing 7.2 g of dimethyldiethoxysilane and methyltriethoxysilane was added dropwise. The mixture was stirred at 70 °C for 5 h. After cooling to room temperature, the reaction mixture was quickly poured into petroleum ether, impurities were filtered out, and the mixture was vacuum distilled to obtain a mixture of dibenzocyclobutenylmethylethoxysilane and dibenzocyclobutenyldiethoxysilane. 50 mL of ethanol and 0.02 g of... Mix 9.28 g of tetramethylamine hydroxide and 5 mL of water until homogeneous. Add a mixture of 9.28 g of dibenzocyclobutenylmethylethoxysilane and dibenzocyclobutenyldiethoxysilane and 3.54 g of dimethyldiethoxysilane. Stir the mixture at 60 °C for 4 h. Cool to room temperature and wash with water until neutral. Dry the organic layer with anhydrous sodium sulfate. Filter to remove toluene. Reduce the pressure and heat to 150 °C / 10 MPa to remove small molecule compounds, yielding organosilicon resin A2 containing benzocyclobutenyl groups.

[0111] (2) Maleimide compounds

[0112] Maleimide compound B1 comprises an addition reaction product of maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and amine compound a2 containing at least two primary amino groups in one molecule. The preparation method is as follows: 2 parts by weight of amine compound Kayahard AA (3,3'-diethyl-4,4'-diaminodiphenylmethane, Nippon Kayaku Co., Ltd.), 18 parts by weight of X-22-161A (a siloxane compound with two primary amino groups at the molecule's end, Shin-Etsu Chemical Co., Ltd.), 20 parts by weight of bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, and 30 parts by weight of solvent propylene glycol monomethyl ether are added to a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. The reaction is maintained at 115°C for 360 min to obtain maleimide compound B1.

[0113] Maleimide compound B2 comprises an addition reaction product of maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and amine compound a2 containing at least two primary amino groups in one molecule. The preparation method is as follows: 2 parts by weight of amine compound Kayahard AA (3,3'-diethyl-4,4'-diaminodiphenylmethane, Nippon Kayaku Co., Ltd.), 16 parts by weight of X-22-161A (a siloxane compound with two primary amino groups at the end of the molecule, Shin-Etsu Chemical Co., Ltd.), 22 parts by weight of 2,2-bis(4-(4-maleimide-phenoxy)phenyl)propane (Yamato Kasei Corporation), and 30 parts by weight of solvent propylene glycol monomethyl ether are added to a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. The reaction is maintained at 115°C for 360 min to obtain maleimide compound B2.

[0114] MIR-3000-70MT, a biphenyl polymaleimide compound, manufactured by Nippon Kayaku Co., Ltd.

[0115] (3) Other resins

[0116] OPE-2st 1200, polyphenylene ether containing vinyl benzyl groups at the end, Mitsubishi Chemical Corporation;

[0117] ODV-XET, multifunctional vinyl compound, Nippon Steel Corporation.

[0118] (4) Thermoplastic polymers

[0119] Tuftec M1913, a hydrogenated styrene-butadiene copolymer with maleic anhydride structural units, Asahi Kasei Chemicals Co., Ltd.

[0120] (5) Inorganic fillers

[0121] SC2500-SXJ, spherical silica modified with aniline-siloxane, average particle size D 50 It is 0.5μm, from Admatechs Co., Ltd., Japan.

[0122] (6) Coupling agent

[0123] KBM-573, phenylaminosilane coupling agent, Shin-Etsu Chemical Industry Co., Ltd.

[0124] (7) Other silicone resins

[0125] X-22-164B, an organosilicon resin containing methacrylic acid groups, Shin-Etsu Chemical Industry Co., Ltd.

[0126] Examples 1-6, Comparative Examples 1-4

[0127] A resin composition, the types and amounts of each component are shown in Tables 1 and 2, and the unit of amount of each component is "parts".

[0128] A prepreg comprising the resin composition and a metal foil-coated laminate are prepared by the following method:

[0129] (1) Mix and disperse each component of the resin composition with toluene solvent according to the formula amount to prepare a resin solution with a solid content of 60%.

[0130] (2) Impregnate the fiberglass cloth (3313L fiberglass cloth manufactured by Hubel, Taiwan, China) with the resin solution, and then heat and dry it in a forced-air oven at 140°C for 5 minutes to transform the resin composition in the varnish state into a semi-cured resin composition, with the single weight controlled at 175 g / m³. 2 To obtain prepreg;

[0131] (3) Stack two (or eight) sheets of prepreg obtained in step (2) together, and press an electrolytic copper foil with a thickness of 12 μm onto the top and bottom sides of the stack. Then press the stack at 220°C and 45 kg / cm² in a press. 2 After curing for 90 minutes, a metal foil laminate with a core board thickness of 0.20 mm (or 0.80 mm) is obtained. After etching the copper foil of the metal foil laminate, a laminate with a thickness of 0.20 mm (or 0.80 mm) is obtained.

[0132] The performance of the metal foil-coated laminate / laminate is tested using the following specific methods:

[0133] (1) Glass transition temperature Tg: A laminate with a length of 60 mm, a width of 10 mm, and a thickness of 0.80 mm was used as a sample and measured using a dynamic mechanical thermal analyzer (DMA) at a heating rate of 10 °C / min. The result was taken as the transition peak temperature of tanδ, in °C.

[0134] (2) Planar thermal expansion coefficient XY-CTE: A laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.20 mm was used as the sample. The glass fiber warp direction was Y-direction, and the glass fiber weft direction was X-direction. The sample was dried in an oven at 105℃ for 1 h and then cooled to room temperature in a desiccator. The mechanical thermal analysis (TMA) method was used for measurement. The heating rate was 10℃ / min. The temperature was increased from room temperature to 200℃ twice. After the first heating was completed and the sample was cooled to room temperature, it was placed again for the second heating. The result was the planar thermal expansion coefficient at the second heating from 60℃ to 120℃, and the unit was ppm / ℃.

[0135] (3) Dielectric constant D k and dielectric loss tangent D f A laminate measuring 100 mm in length, 100 mm in width, and 0.20 mm in thickness was used as a sample. After ultrasonic cleaning to remove surface impurities in deionized water, the sample was dried in a 105°C oven for 1 hour and then cooled to room temperature in a desiccator. The dielectric constant (Dk) at a frequency of 10 GHz was measured using a cavity resonator. k ) and dielectric loss tangent (D f );

[0136] The dielectric loss tangent D after moisture absorption f Take the loss tangent of the above-mentioned test medium (D) f The sample was placed in an environment of 25°C and 55% humidity for one week, and the dielectric loss tangent (D) at a frequency of 10 GHz was measured using a cavity resonator. f );

[0137] (4) Water absorption rate: A laminate with a length of 50 mm, a width of 50 mm, and a thickness of 0.80 mm was taken as a sample. After the impurities on the surface of the sample were removed by ultrasonic cleaning in deionized water, it was dried in an oven at 105℃ for 1 hour and weighed as W0. The sample was then soaked in water at 25℃ for 24 hours, removed and air-dried, and weighed as W1. Water absorption rate = 100% × (W1 - W0) / W0.

[0138] (5) PCT (Potential Pressure Test): A laminate with a length of 50 mm, a width of 50 mm, and a thickness of 0.8 mm is used as a sample. The sample is treated in a high-pressure tester at 121°C and two atmospheres for 5 hours. Then the sample is immersed in tin in a tin bath at 288°C and the time without bubbling is recorded. If it is greater than 300s, the heat resistance is passed. Three samples are tested for each example or comparative example. If the heat resistance of one sample passes, it is recorded as "2 / 3". If the heat resistance of three samples passes, it is recorded as "0 / 3", and so on.

[0139] (6) Compatibility assessment: Obtain the resin composition in clear varnish state according to the proportions in Table 1 and Table 2, and place it in a 40mL measuring container. If the resin composition in clear varnish state is observed to be turbid, it is judged as "incompatible"; otherwise, it is judged as "compatible". If the resin composition in clear varnish state is observed to be clear, it is sealed and left to stand for 1 day. After 1 day, the resin phase separation is observed again. If the resin is phase separated and one of the phases is rubbery, it is judged as "incompatible"; otherwise, it is judged as "compatible".

[0140] The test results are shown in Tables 1 and 2.

[0141] Table 1

[0142]

[0143]

[0144] Table 2

[0145]

[0146]

[0147] Based on the aforementioned performance test data, it can be seen that the present invention, through the design of a specific structure of benzocyclobutene-containing organosilicon resin, a specific maleimide compound, and its mutual compounding with other resins, enables the cured resin composition to possess a high glass transition temperature, a low coefficient of thermal expansion, a low water absorption rate, a low dielectric constant, and a low dielectric loss tangent. The dielectric constant D of the metal foil laminates in Examples 1-6 at 10 GHz is shown. k The dielectric loss tangent D is 3.45-3.61. f The coefficient of thermal expansion (XY-CTE) is 0.0030-0.0037, the coefficient of thermal expansion (XY-CTE) is 8-11 ppm / ℃, the glass transition temperature (Tg) is 235-281℃, and the water absorption rate is 0.10-0.17%. It combines low thermal expansion coefficient, low water absorption rate, excellent dielectric properties, heat resistance, and resistance to damp heat. This solves the problem of large changes in the dielectric loss tangent and high water absorption rate after moisture absorption in cured resin compositions. The dielectric loss tangent D after moisture absorption... f With a variation value ≤0.0005, it is especially suitable for applications with high requirements for heat resistance and dielectric loss under different environments, such as high-speed packaging substrate materials.

[0148] Compared with Example 1, Comparative Example 1 used a silicone resin containing methacrylic acid groups. Since a silicone resin containing benzocyclobutene groups was not used, the glass transition temperature of the resin composition was worse and the coefficient of thermal expansion was increased due to insufficient crosslinking density. The silicone resin in the resin composition showed agglomeration and phase separation. The metal foil laminate failed the tin immersion test after PCT treatment.

[0149] Compared with Example 1, Comparative Example 2 used a biphenyl polymaleimide compound. Because it did not use the addition reaction product of maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and amine compound a2 containing at least two primary amino groups in one molecule, the resin composition in the clear state had insufficient compatibility due to the large polarity difference. The metal foil laminate failed the tin-immersion test after PCT treatment.

[0150] Compared to Example 1, the content of the benzocyclobutene-containing silicone resin in Comparative Example 3 was too low. Therefore, the resin composition exhibited a high water absorption rate and low water absorption D due to insufficient silicone resin content and insufficient crosslinking density. f The rate of change increased; compared with Example 1, the content of benzocyclobutene-containing organosilicon resin in Comparative Example 4 was too high. As a result, the resin composition had a lower glass transition temperature and a higher coefficient of thermal expansion due to insufficient content of maleimide resin with high heat resistance.

[0151] The applicant declares that the above embodiments illustrate the resin composition, metal foil laminate, and their applications, but the present invention is not limited to the above embodiments, i.e., it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components in parts by weight: 10-40 parts of organosilicon resin containing benzocyclobutene group 40-90 parts of maleimide compound Other resins: 10-50 parts; The organosilicon resin containing benzocyclobutene includes any one or a combination of at least two of the resins shown in Formula I, Formula II, and Formula III. R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from any one of hydrogen, C1-C18 straight-chain or branched alkyl, C3-C10 cycloalkyl, C2-C6 alkenyl, C6-C12 aryl, and C2-C12 heteroaryl. m, p, and a are each independent numbers ≥ 2, and n, q, and b are each independent numbers ≥ 0; The maleimide compound comprises an addition reaction product of a maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and an amine compound a2 containing at least two primary amino groups in one molecule.

2. The resin composition according to claim 1, characterized in that, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from any one of C1-C12 straight-chain or branched alkyl, C2-C4 alkenyl, and C6-C12 aryl, preferably any one of methyl, ethyl, n-propyl, isopropyl, allyl, phenyl, and dodecyl. Preferably, 0.1≤m / (m+n)≤0.8, 0.1≤p / (p+q)≤0.8, and 0.1≤a / (a+b)≤0.8; Preferably, the number-average molecular weight of the organosilicon resin containing benzocyclobutene is 500-20000.

3. The resin composition according to claim 1 or 2, characterized in that, The maleimide compound a1 contains two N-substituted maleimide groups in one molecule; Preferably, the maleimide compound a1 includes N,N'-ethylidene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,3-(2-methylphenylene))bismaleimide, N,N'-(1,3-(4-methylphenylene))bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimide-phenyl)methane, bis(3-methyl-4-maleimide-phenyl)methane, bis(3,5-dimethyl-4-maleimide-phenyl)methane, and bis(3-ethyl-5-methyl-4-maleimide-phenyl) Methane, bis(3-ethyl-4-maleimide-phenyl)methane, bis(3,5-diethyl-4-maleimide-phenyl)methane, bis(4-maleimide-phenyl) ether, bis(4-maleimide-phenyl) ketone, bis(4-maleimide-cyclohexyl)methane, 1,4-bis(4-maleimide-phenyl)cyclohexane, 1,4-bis(maleimide-methyl)cyclohexane, 1,4-bis(maleimide-methyl)benzene, 1,3-bis(4-maleimide-phenoxy)benzene, 1,3-bis(3-maleimide-phenoxy)benzene, bis(4-(3-maleimide-phenoxy)phenyl)methane, bis(4-(4-maleimide-phenyl) 1,1-bis(4-(3-maleiminophenoxy)phenyl)ethane, 1,1-bis(4-(4-maleiminophenoxy)phenyl)ethane, 1,2-bis(4-(3-maleiminophenoxy)phenyl)ethane, 1,2-bis(4-(4-maleiminophenoxy)phenyl)ethane, 2,2-bis(4-(3-maleiminophenoxy)phenyl)propane, 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane, 2,2-bis(4-(3-maleiminophenoxy)phenyl)butane, 2,2-bis(4-(4-maleiminophenoxy)phenyl)butane, 4,4' -A combination of any one or at least two of the following: bis(3-maleiminophenoxy)biphenyl, 4,4'-bis(4-maleiminophenoxy)biphenyl, bis(4-(3-maleiminophenoxy)phenyl)one, bis(4-(4-maleiminophenoxy)phenyl)one, bis(4-(3-maleiminophenoxy)phenyl)ether, and bis(4-(4-maleiminophenoxy)phenyl)ether; further preferably, a combination of any one or at least two of the following: bis(3-ethyl-5-methyl-4-maleiminophenyl)methane, bis(4-maleiminophenyl)methane, and 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane; Preferably, the amine compound a2 comprises a siloxane compound containing at least two primary amino groups, diaminobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,3'-diethyl-4,4'-diaminodiphenylmethane. 4'-Diaminodiphenylmethane, 3,3'-Diethyl-5,5'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-5,5'-Diethyl-4,4'-Diaminodiphenylmethane, diaminodiphenyl ether, 3,3'-Dimethoxy-4,4'-Diaminodiphenyl ether, 3,3'-Dimethyl-4,4'-Diaminodiphenyl ether, 3,3'-Dimethyl-5,5'-Dimethyl-4,4'-Diaminodiphenyl ether, 3,3'-Diethyl-4,4'-Diaminodiphenyl ether, 3,3'-Diethyl-5,5'-Diethyl 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl; further The preferred step involves any one or a combination of at least two of the following: a siloxane compound containing at least two primary amino groups; 3,3'-dimethyl-4,4'-diaminodiphenylmethane; 3,3'-dimethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane; 3,3'-diethyl-4,4'-diaminodiphenylmethane; 3,3'-diethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane; 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane; and 2,2-bis(4-(4-aminophenoxy)phenyl)propane.

4. The resin composition according to any one of claims 1-3, characterized in that, The other resins include any one or a combination of at least two of epoxy resins, acid anhydride compounds, active ester compounds, cyanate ester compounds, and compounds having carbon-carbon unsaturated double bonds in their molecules, preferably compounds having carbon-carbon unsaturated double bonds in their molecules. Preferably, the compound having carbon-carbon unsaturated double bonds in the molecule includes any one or a combination of at least two of the following: unsaturated polyphenylene ether, polyfunctional vinyl compounds, allyl compounds, acrylate compounds, acenaphthene compounds, and polybutadiene; Preferably, the resin composition further comprises 5-30 parts by weight of a thermoplastic polymer; Preferably, the thermoplastic polymer includes any one or a combination of at least two of styrene-based polymers, hydrogenated styrene-based polymers, and polyolefin resins; Preferably, the resin composition further comprises 0.01-5 parts by weight of a curing accelerator; Preferably, the curing accelerator includes any one or a combination of at least two of the following: acidic curing accelerators, organophosphorus curing accelerators, imidazole curing accelerators, pyridine curing accelerators, amine curing accelerators, peroxides, and organometallic salts. Preferably, the resin composition further comprises 5-250 parts by weight of inorganic filler; Preferably, the resin composition further comprises 2-50 parts by weight of flame retardant; Preferably, the resin composition further comprises 0.01-10 parts by weight of coupling agent; Preferably, the coupling agent comprises a silane coupling agent.

5. A resin film, characterized in that, The resin film is made of the resin composition as described in any one of claims 1-4; Preferably, the resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

6. A resin-coated copper foil, characterized in that, The resin-coated copper foil comprises a copper foil layer and a resin layer, wherein the material of the resin layer comprises the resin composition as described in any one of claims 1-4.

7. A prepreg, characterized in that, The prepreg comprises a substrate and a resin composition as described in any one of claims 1-4 attached to the substrate; Preferably, the resin composition is adhered to the substrate after impregnation and drying.

8. A laminate, characterized in that, The laminate comprises at least one sheet of prepreg as described in claim 7.

9. A metal foil-coated laminate, characterized in that, The metal foil laminate includes at least one of the resin film as described in claim 5, the resin-coated copper foil as described in claim 6, and the prepreg as described in claim 7.

10. A printed circuit board, characterized in that, The printed circuit board includes at least one of the following: the resin film as described in claim 5, the resin-coated copper foil as described in claim 6, the prepreg as described in claim 7, the laminate as described in claim 8, and the metal foil-coated laminate as described in claim 9.

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